minerals

Article
Comparative Study on Surface Structure,
Electronic Properties of Sulfide and Oxide Minerals:
A First-Principles Perspective
Weiyong Cui 1 , Yibing Zhang 2 , Jianhua Chen 1,3,4, *, Cuihua Zhao 3 , Yuqiong Li 3,4 , Ye Chen 3,4
and Ming-Hsien Lee 5
1 College of Chemistry and Chemical Engineering, Guangxi University, Nanning 530004, China;
wei_yung@163.com
2 Guizhou Daliang Zinc Industry Co., Ltd., Duyun 558000, China; zybflad@163.com
3 School of Resources, Environment and Materials, Guangxi University, Nanning 530004, China;
xiaocui2000110@163.com (C.Z.); lyq198205@163.com (Y.L.); fby18@126.com (Y.C.)
4 Guangxi Key Laboratory of Processing for Non-ferrous Metal and Featured Materials, Guangxi University,
Nanning 530004, China
5 Department of Physics, Tamkang University, New Taipei 25137, China; mhslee@mail.tku.edu.tw
* Correspondence: jhchen@gxu.edu.cn




Received: 17 April 2019; Accepted: 18 May 2019; Published: 28 May 2019


Abstract: First-principle calculations were used to investigate the surface structure and electronic
properties of sulfide (pyrite, galena, and sphalerite) and oxide minerals (hematite, cerussite,
and smithsonite). Surface relaxation and Femi energy, as well as projected DOS, are considered.
Results show that the surface atoms of the sulfide minerals are more susceptible and more easily
affected by the fracture bonds. The sulfide surfaces possess higher chemical potential than the
corresponding oxide surfaces, and are more likely to be electron donors in reactions. The S 3p states
are the mainly contributing states in the sulfide surface, while that in the oxide surface are O 2p states.
The bonds of the sulfide surface have more covalent features and that of the oxide surface are ionic
interactions. The O–M (M represents Fe, Pb or Zn) bonds are more stable, as the DOS of the oxide
surfaces distribute in the lower energy range.

Keywords: sulfide minerals; oxide minerals; surface electronic properties; density functional
theory (DFT)

1. Introduction
Flotation is the most important and versatile mineral separation technique, which provides
raw materials for our metallurgical and chemical industries [1]. For the nonferrous metals industry,
flotation is an indispensable technique and usually used to enrich minerals, such as lead and zinc
minerals. Comparatively speaking, the flotation operation of sulfide minerals is mature and has been
well applied in plants around the world. The oxide minerals flotation is more difficult and complex
than that of the corresponding sulfide minerals due to the surface hydrophilicity and electrostatic
interaction [2]. However, the condition has become much more complicated with the depletion of the
easy separation sulfide ore resources and the increasingly stringent environmental costs.
It is not a new topic that different surface properties lead to significant differences in flotation
behaviors. The investigations about surface structure and properties of sulfide and oxide minerals
are not rare, and corresponding papers include ultraviolet photoelectron spectroscopy (UPS) [3,4],
Raman spectroscopy [5], scanning tunneling microscopy (STM) [3,6], time of flight secondary ion mass
spectrometry, (ToF–SIMS) [6,7], x-ray photoelectron spectroscopy (XPS) [8–11], DFT studies [8,9,12–14],

Minerals 2019, 9, 329; doi:10.3390/min9060329 www.mdpi.com/journal/minerals

Minerals 2019, 9, 329 2 of 12

etc. Recently, reports with density functional theory method (DFT) triggered intense research in this
area. G. U. von Oertzen and W. M. Skinner found that the quantum chemical simulation predicts an S
2p core level shift of 0.69 eV between the S bulk and S surface dimers, in good agreement with the 0.6 eV
found in XPS measurements [15]. A series of studies by Chen et al. confirmed that the lattice defects in
sulfide minerals surface have significant effect on the properties of flotation [16–21]. Cong Han et al.
found that the O atom on the hemimorphite (110) surface exhibits stronger ability on impeding the
collector bond with the Zn atoms than that on the smithsonite (101) surface [13]. The research by
Feng et al. showed that the active sites on the cerussite (110) surface are Pb atoms, which mainly
contribute by the Pb 6p orbital [9]. However, a comprehensive research about the different structure
and electronic properties of sulfide and oxide minerals surfaces has not been conducted.
As the most common and important minerals, lead, zinc, and iron ore widely exist in various
sulfide and oxide minerals, which are usually found in mixtures or in combination with other minerals,
and their nature differences have troubled us for many years. In this paper, the comparative study of
sulfide and oxide minerals surface is considered, and three groups of representative mineral surface
models (pyrite (100) and hematite (001) surfaces, galena (100) and cerussite (110) surfaces, as well as
sphalerite (110) and smithsonite (101) surfaces) are chosen [22–26]. The surface relaxation, Femi energy
and projected density of states (projected DOS) are discussed. It is expected that this research is of high
interest for understanding the surface structure and electronic properties of sulfide and oxide minerals,
and providing the theoretical basis for surface interaction.

2. Computational Methods and Models

2.1. Computational Methods

All calculations were performed using the density-functional theory (DFT) with Cambridge
Serial Total Energy Package [27]. Ultra-soft pseudo-potential was used to describe electron–ion
interactions. The exchange correlation functional used in pyrite and smithsonite models was GGA-PBE
and GGA-PW91 in hematite and galena models, and GGA-WC and GGA-RPBE in cerussite and
sphalerite models, respectively. The plane-wave cutoff energy of 280 eV for pyrite, 220 eV for hematite
and galena, 260 eV for cerussite and smithsonite, and 285 eV for sphalerite were used throughout.
Monkhorst-Pack k-point sampling density for pyrite and galena was 2 × 2 × 1 mesh, 1 × 1 × 1 for
hematite, cerussite, and smithsonite, and 2 × 3 × 1 for sphalerite. The Hubbard U value of 7.5 eV was
adopted, and the spin-polarized in the pyrite and hematite models was chosen. The convergence
tolerances for geometry optimization calculations were set to the maximum displacement of 0.002 Å,
the maximum force of 0.05 eV·Å−1 , the maximum energy change of 2.0 × 10 −5 eV·atom−1 , and the
maximum stress of 0.1 GPa, and the SCF convergence tolerance was set to be 2.0 × 10−6 eV·atom−1 .
Valence electron configurations considered in the research were O 2s2 2p4 , C s2 2p2 , S 3s2 3p4 , Fe 3d6 4s2 ,
Pb 6s2 6p2 , and Zn 3d10 4s2 . The vacuum thickness in the surfaces was 10 angstroms, which could
essentially meet the calculation.

2.2. Computational Models

The bulk models were optimized, and the results are in good agreement with the experimental
results (see Table 1). The surface models were cleaved from the corresponding optimized bulk models
and the most stable surface models were chosen.
Minerals 2019, 9, 329 3 of 12

Table 1. The comparison between the lattice parameters of the optimized model and the experimental
results of the bulk.

Experimental Value Calculated Value (% Difference)

Minerals
a/Å b/Å c/Å a/Å b/Å c/Å
Minerals 2019, 9, x FOR PEER REVIEW 3 of 13
pyrite 5.428 5.428 5.428 5.407(0.39%) 5.407(0.39%) 5.407(0.39%)
hematite 5.038 5.038 13.772 5.109(1.41%) 5.109(1.41%) 13.970(1.49%)
Table 1. The comparison between the lattice parameters of the optimized model and the experimental
results of the
galena bulk.
5.914 5.914 5.914 5.832(1.39%) 5.832(1.39%) 5.832(1.39%)
cerussite 5.182 Experimental
8.495 Value6.144 5.194(0.23%) 8.50(0.06%)
Calculated Value (% Difference) 6.17(0.42%)
Minerals
a/Å b/Å
c/Å a/Å b/Å c/Å
sphalerite 5.409 5.409
5.409 5.326(1.53%) 5.326(1.53%) 5.326(1.53%)
pyrite 5.428 5.428
5.428 5.407(0.39%) 5.407(0.39%) 5.407(0.39%)
smithsonite
hematite
4.653
5.038
4.653
4.653
5.038
13.772
4.712(1.27%)
5.109(1.41%)
4.712(1.27%)
5.109(1.41%)
4.712(1.27%)
13.970(1.49%)
galena 5.914 5.914 5.914 5.832(1.39%) 5.832(1.39%) 5.832(1.39%)
cerussite 5.182 8.495 6.144 5.194(0.23%) 8.50(0.06%) 6.17(0.42%)
As shownsphalerite
in Figure 1a,
5.409pyrite
5.409(100)5.409
surface5.326(1.53%)
with twelve atomic layers is
5.326(1.53%) constructed and the
5.326(1.53%)
coordination numbers of the exposed Fe and S atoms are five and three, respectively. Slab model
smithsonite 4.653 4.653 4.653 4.712(1.27%) 4.712(1.27%) 4.712(1.27%)

with 18 atomic layers of hematite (001) surface is shown in Figure 1b. Each Fe atom of the surface
As shown in Figure 1a, pyrite (100) surface with twelve atomic layers is constructed and the
coordinatescoordination
with three adjacent
numbers of theO atoms,
exposed andS the
Fe and atoms exposed
are five andOthree,
atom connectsSlab
respectively. with thewith
model nearest three
Fe atoms. Figure
18 atomic1clayers
shows of the slab(001)
hematite model of six
surface atomic
is shown in layers of galena
Figure 1b. Each Fe (100)
atom of surface. The Pb atom
the surface
coordinates
of the surface bond withwith three
fiveadjacent
S atoms,O atoms,
andandthethe exposed O atomnumber
coordination connects with
of thethe outmost
nearest three
S Fe
atom is also
atoms. Figure 1c shows the slab model of six atomic layers of galena (100) surface. The Pb atom of the
five. Figuresurface
1d presents the 12 atomic layers of cerussite (110) surface, and the
bond with five S atoms, and the coordination number of the outmost S atom is also five.
central Pb atom has
a coordination number
Figure of four,
1d presents while
the 12 thelayers
atomic O atom coordinates
of cerussite with adjacent
(110) surface, four Pb
and the central Pb atom
atoms.has As
a shown in
Figure 1e, acoordination
sphaleritenumber of four, while
(110) surface withthe 10Oatomic
atom coordinates
layers iswithbuiltadjacent four Pb
and each atoms. As
exposed Znshown
(S) coordinates
in Figure 1e, a sphalerite (110) surface with 10 atomic layers is built and each exposed Zn (S)
with adjacent three S (Zn). For the smithsonite (101) surface (see Figure 1f), the exposed outer Zn atom
coordinates with adjacent three S (Zn). For the smithsonite (101) surface (see Figure 1f), the exposed
coordinatesouter
withZnfive
atomOcoordinates
atoms and withthe
fiveOOatom
atoms has a coordination
and the number of
O atom has a coordination two.of two.
number

Figure of
Figure 1. Slabs 1. Slabs of represent
represent minerals
minerals surfaces: (a)(a)
surfaces: Pyrite (100)(100)
Pyrite surface; (b) hematite
surface; (b)(001) surface; (001)
hematite (c) surface;
galena (100) surface; (d) cerussite (110) surface; (e) sphalerite (110) surface; (f) smithsonite (101)
(c) galena (100) surface; (d) cerussite (110) surface; (e) sphalerite (110) surface; (f) smithsonite
surface.
(101) surface.
3. Results and Discussions
3. Results and Discussions
3.1. Surface Relaxation
3.1. Surface Relaxation
Surface atoms will rearrange themselves spontaneously when a new surface is cleaved, and this
Surfacehasatoms
been confirmed in many reports [28–30]. The atom displacements of different surfaces are
will rearrange themselves spontaneously when a new surface is cleaved, and this
presented in Table 2.
has been confirmed in many reports [28–30]. The atom displacements of different surfaces are presented
in Table 2.
For the pyrite (100) surface, the Fe and S atoms converge heavily toward the bulk with the
displacements of −4.83 pm and −8.72 pm in the z-direction. Meanwhile, the opposite level displacements
Minerals 2019, 9, 329 4 of 12

indicate that the two atoms move away from each other in the x-y plane. Atomic displacements of
the hematite (001) surface are more complex than that of the pyrite (100) surface. The movements
of O atoms are −10.82~8.75 pm and −4.17~10.42 pm in the x and y directions. The Fe mainly shows
convergence along the z direction with the shift of −55.03 pm, which corresponds to the fact that the
three broken bonds of the Fe atom are z-axis of rotation.
Interestingly, the main displacement of atoms in the galena (100) surface is from the z direction,
which is related to the unique crystal structure and the broken bonds along the z-direction.
The corresponding values of S and Pb atoms are 20.56 pm and 15.24 pm, respectively, which confirms
that the severe interlayer atomic interactions and reconstructions occur in the galena (100) surface.
Although there are serious bonds breaking in the cerussite (110) surface and the coordination number
of Pb is reduced from 7 to 4, the displacements of the Pb and O atoms are rather small and no apparent
surface reconstruction is found, implying that the interaction of the O–Pb bond is very strong.
For the sphalerite (110) surface, serious reconstruction can be seen, and the Zn and S atoms are
shifted heavily in three-dimensional space. Atomic movement of the S and Zn is as large as 44.20 pm
and −22.91 pm in z-direction, while that along the x and y directions also reach about 10 pm respectively,
indicating that the S–Zn bond is greatly affected in the (110) surface. In the smithsonite (101) surface,
the displacement of each atom is very small and cannot cause remarkable change, though there exists
small shift in the surface.

Table 2. Atomic displacements of the minerals surface.

Displacement/pm
Minerals Atoms
∆x ∆y ∆z
S −2.77 −6.82 −4.83
Pyrite (100)
Fe 3.82 4.28 −8.72
Fe 0.23 0.04 −55.03
Hematite (001)
O −10.82~−8.75 −4.17~−10.42 −1.63~−0.96
S 0.00 0.00 20.56
Galena (100)
Pb 0.00 0.00 15.24
O −0.13~−0.05 −0.17~−0.15 −0.28~−0.25
Cerussite (110)
Pb 0.04~0.09 0.00~0.05 −0.43~−0.20
S 7.20 −8.30 44.20
Sphalerite (110)
Zn −12.45 −11.64 −22.91
O 0.04 2.24 3.07
Smithsonite (101) O 1.77 −1.24 1.20
Zn −1.59 1.46 −2.67

3.2. Femi Energy

The Femi level shows the filling capacity of electrons, which often represents electron or hole
chemical potentials, and can be defined as Equation (1):

∂G
!
Ef = µ = (1)
∂N T,p

where µ represents chemical potentials, G is the Gibbs free energy, N refers to the sum of the electrons
of the whole system, and T and p represent temperature and pressure of the system, respectively.
The Femi level can reveal the ability of redox of the microsystem and reports show it can be well
agreement with standard potential [31]. The higher Fermi energy system is more likely to transfer
electrons and lower its Femi level to make the system more stable. As shown in Table 3, the Femi levels
of pyrite (100) surface and hematite (001) surface are 0.3687 eV and −2.469 eV, respectively, which
means that the pyrite (100) surface has higher chemical potential, and the result is consistent with
Minerals 2019, 9, 329 5 of 12

the measurement of redox potential [32]. For the galena and cerussite system, the Femi energy of the
galena (100) surface is 3.957 eV and the corresponding value of the cerussite (110) surface is −0.881 eV,
that is, cerussite (110) surface is not as easy to transfer electrons as galena (100) surface, which was
proven by Herrera-Urbinaa et al. with the pulp redox potential research [33]. Meanwhile, the Femi
energy of the smithsonite (101) surface is also lower than that of the sphalerite (110) surface, indicating
that the sphalerite surface has advantage as electron donors in chemical reaction, and this has been
reported in many papers [34,35].

Table 3. The calculated Femi level of the minerals surface.

Surface /eV
Pyrite (100) 0.3687
Hematite (001) −2.469
Galena (100) 3.9567
Cerussite (110) −0.881
Sphalerite (110) 1.2051
Smithsonite (101) −1.047

3.3. Surface Electronic Structure

3.3.1. Surface Properties of Pyrite (100) and Hematite (001) Surfaces

The projected DOSs of S and Fe atoms in the pyrite (100) surface are presented in Figure 2. For the
S center, the S–Fe broken bond shows the largest component along the z-direction. Strong splits occur
in the S 3p states, the 3px , 3py , and 3pz states are rather different. The 3pz state has more distributions
in the upper valence band, and its peaks at −2.25 eV, −0.81 eV, and −0.12 eV are much higher. In the Fe
center, the Fe 3px , 3py , and 3pz are also different, and the 3pz state possesses sharp peaks at 0.76 eV,
4.88 eV, and 5.61 eV. The Fe 3d states are divided into three groups, the 3dx 2 −y 2 , the 3dz 2 , and the
3dxy –3dxz –3dyz states. The 3dxy –3dxz –3dyz states are slightly split below Femi level and dominate the
VBM, while the CBM are mainly contributed by 3dz 2 state. The 3dx 2 −y 2 state is not split, however,
the 3dz 2 states has more distributions near Femi level, which is proven by the fact that there has high
activity along z-direction in the dangling bond.
The overlaps between S and Fe atoms are mainly from the contribution of S 3p and Fe 3p, 3d
states. The bonding interactions are in the range of −7.5 to −1.50 eV, which is contributed by S 3p (3px ,
3py and 3pz ) and Fe 3dx 2 −y 2 , 3dz 2 , as well as 3dxy states. Significant antibonding areas are found near
Femi level, and the interaction of S 3pz and Fe 3dxy , 3dxz , and 3dyz states are very strong in the range
from −1.25 to 0 eV, while the mixings of the S 3s, 3p, and Fe 3pz , 3dz 2 , and 3dxz states are in the range
from 0.37 to 1.50 eV. Meanwhile, complex mixings are found in the conduction band areas far away
from Femi level.
Figure 3 shows the projected DOSs of O and Fe atoms for hematite (001) surface. The O 2p states
show obvious localization, and can be divided into two parts, the 2px , 2py states and 2pz state. The 2px ,
2py states are slightly disturbed and their curves seem to be similar, while the 2pz state is heavily split
and its peak at −5.5eV is sharp. There are three O–Fe bonds broken in the Fe atom and the interactions
of the other O–Fe bonds become strong. As shown in Figure 3b, the Fe 3pz state is split heavily below
the Femi level and shows apparent difference with the other two 3p states in the range from −7.0 to
−3.0 eV. The octahedron field is destroyed, and the 3d states are divided into three parts (Figure 3c,d),
the 3dx 2 −y 2 and 3dxy states, the 3dxz and 3dyz states, and the 3dz 2 state. The 3dx 2 −y 2 and 3dxy states
mainly distribute in high energy with the peaks at −9.3 eV, −8.85 eV, −5.6 eV, and −4.45 eV, the 3dxz and
3dyz states shows a slight split and their peaks are mainly in the range from −9.5 to −4.0eV, while the
3dz 2 state is split heavily and its curve is in lower energy with remarkable peaks at −9.65 eV, −7.30 eV,
and −6.5 eV.
Minerals 2019, 9, 329 6 of 12
Minerals 2019, 9, x FOR PEER REVIEW 6 of 13

Figure 2. Projected DOSs of S and Fe atoms of pyrite (100) surface: (a) S 3s, 3px , 3py and 3pz states;
Figure
Minerals 2019, 2.
9, xProjected
FOR PEER DOSs of S and Fe atoms of pyrite (100) surface: (a) S 3s, 3px, 3py and 3pz states; (b)
REVIEW 7 of 13
2 2
(b) Fe 4s, 3px , 3py and 3pz states; (c) Fe23d2 x –y and 2
3dz states; (d) Fe 3dxy , 3dxz and 3dyz states.
Fe 4s, 3px, 3py and 3pz states; (c) Fe 3dx –y and 3dz2 states; (d) Fe 3dxy, 3dxz and 3dyz states.

Figure 3 shows the projected DOSs of O and Fe atoms for hematite (001) surface. The O 2p states
show obvious localization, and can be divided into two parts, the 2px, 2py states and 2pz state. The
2px, 2py states are slightly disturbed and their curves seem to be similar, while the 2pz state is heavily
split and its peak at −5.5eV is sharp. There are three O–Fe bonds broken in the Fe atom and the
interactions of the other O–Fe bonds become strong. As shown in Figure 3b, the Fe 3pz state is split
heavily below the Femi level and shows apparent difference with the other two 3p states in the range
from −7.0 to −3.0 eV. The octahedron field is destroyed, and the 3d states are divided into three parts
(Figure 3c, d), the 3dx2−y2 and 3dxy states, the 3dxz and 3dyz states, and the 3dz2 state. The 3dx2−y2 and 3dxy
states mainly distribute in high energy with the peaks at −9.3 eV, −8.85 eV, −5.6 eV, and −4.45 eV, the
3dxz and 3dyz states shows a slight split and their peaks are mainly in the range from −9.5 to −4.0eV,
while the 3dz2 state is split heavily and its curve is in lower energy with remarkable peaks at −9.65 eV,
−7.30 eV, and −6.5 eV.

Figure 3. Projected DOSs of O and Fe for hematite (001) surface: (a) O 2s, 2px , 2py and 2pz states; (b) Fe
Figure 3. Projected DOSs of O and Fe for hematite (001) surface: (a) O 2s, 2px, 2py and 2pz states; (b)
4s, 3px , 3py and 3pz states; (c) Fe 3dx 2 –y2 2 ,2 3dz 22 and 3dxy states; (d) Fe 3dxz and 3dyz states.
Fe 4s, 3px, 3py and 3pz states; (c) Fe 3dx –y , 3dz and 3dxy states; (d) Fe 3dxz and 3dyz states.

The Femi level situates at −2.469 eV. The interactions of O and Fe are mainly in the valence band
areas, and the sharp mixing peaks attributing to O 2p and Fe 3p, 3d, and 4s orbitals show more
characteristic of localization. Significant bonding interactions are located in the range from −8.25 to
−7.25 eV, from −6.25 to −4.75 eV and from −3.5 to −2.0 eV, which is contributed by O 2p and 3dzx, 3dzy
 Minerals 2019, 9, 329 7 of 12

The Femi level situates at −2.469 eV. The interactions of O and Fe are mainly in the valence
band areas, and the sharp mixing peaks attributing to O 2p and Fe 3p, 3d, and 4s orbitals show more
characteristic of localization. Significant bonding interactions are located in the range from −8.25 to
−7.25 eV, from −6.25 to −4.75 eV and from −3.5 to −2.0 eV, which is contributed by O 2p and 3dzx , 3dzy
states, O 2pz, and Fe 3dx 2 −y 2 , 3dxy , 3dyz , 3dxz , states as well as O 2px , 2pz , and Fe 3dx 2 −y 2 , 3dxy states.

3.3.2. Surface Properties of Galena (100) and Cerussite (110) Surfaces

Figure 4 shows the projected DOSs of S and Pb atoms in the galena (100) surface. For the central S
atom, the only broken bond is along the z-direction, which has less influence on the x-y plane. For the
S 3p states, the 3px and 3py states have little split and are equivalent states, as they show the same
feature, while the 3pz state is significantly split and its peaks in the upper valence band is quite high
and sharp, indicating its great activity. The bond breakage in the Pb center is similar to that in the S
atom. The Pb 6s state is broadened and more delocalization, and its curves cover in the range from
−7.5 eV to −5.0 eV and from 3.5 eV to 6.7 e V. Three Pb 6p states show same curve outlines, which
means that the 6px , 6py , and 6pz states are also degenerate orbitals, and their DOS are located in the
range from −0.75 eV to 2.10 eV and from 5.50 eV to 7.30 eV.
The interactions between S and Pb are mainly from the contribution of the S 3s, 3p, and Pb 6p
states. The bonding mixings distribute in the range from −0.75 eV to 2.10 eV, while the antibonding
interactions
Minerals are located
2019, 9, x FOR in the energy range from 5.50 eV to 7.30 eV. In addition, there still exist unpaired
PEER REVIEW 8 of 13
Pb 6s states near Femi level.

Figure 4. Projected DOSs of S and Pb of galena (100) surface: (a) S 3s, 3p , 3p and 3p states; (b) Pb 6s,
x y z
Figure 4. Projected DOSs of S and Pb of galena (100) surface: (a) S 3s, 3px, 3py and 3pz states; (b) Pb 6s,
6px , 6py and 6pz states.
6px, 6py and 6pz states.

Figure 5 shows the projected DOSs of O and Pb atoms in the cerussite (110) surface. There is only
one O–Pb bond broken in the O center. The O 2p states are disturbed heavily, and the 2px, 2py, and
2pz states show rather different distributions. There are significantly peaks contributed by 2py and
 Minerals 2019, 9, 329 8 of 12

Figure 5 shows the projected DOSs of O and Pb atoms in the cerussite (110) surface. There is only
one O–Pb bond broken in the O center. The O 2p states are disturbed heavily, and the 2px , 2py , and 2pz
states show rather different distributions. There are significantly peaks contributed by 2py and 2pz
states near Femi level, which implies the activity in the x and z direction. The broken O–Pb bonds in
the Pb atoms is 3. It is found that the splitting of Pb 6s states is not so significant with three apparent
DOS peaks in the range from −10 eV to −6.25 eV. The Pb 6px , 6py , and 6pz states are notably split and
the peaks from 2px , 2py , and 2pz states show different distributions, and the 2pz state has a peak near
Femi level, but not that high and sharp.
The bonding
Minerals 2019, 9, x FOR and antibonding interactions are mainly contributed by O 2p and Pb 6p states in the
PEER REVIEW 9 of 13
range from −10 to 0.5 eV. The bonding mixing peaks attributing by O 2p and Pb 6p states in the upper
valence band near Femi level are very strong. Meanwhile, the obvious localization of the O 2p and Pb
6p states indicate that the interaction of O and Pb has more ionic bond characteristics.

Figure 5. Projected DOSs of O and Pb of cerussite (110) surface: (a) O 2s, 2px , 2py and 2pz states; (b) Pb
Figure 5. 6s, 6px , 6pyDOSs
Projected and 6pzof
states.
O and Pb of cerussite (110) surface: (a) O 2s, 2px, 2py and 2pz states; (b)
Pb 6s, 6p x, 6p
3.3.3. y and Properties
Surface 6pz states.of Sphalerite (110) and Smithsonite (101) Surfaces
The projected DOSs of S and Zn atoms in the sphalerite (101) surface are shown in Figure 6.
3.3.3. Surface
TheProperties of Sphalerite
broken S–Zn bond of the S atom(110)
make and Smithsonite
the S 3p (101)
orbitals no longer Surfaces
balanced. As shown in Figure 6a,
there are significant split of the S 3p states, and the 3py state shows a dramatic difference with the 3px
The projected DOSs
and 3pz states. Forof S 3p
the and Zn atoms in the sphalerite (101) surface are shown in Figure 6. The
x and 3pz states, their curves cover from −5.5 to 1.0 eV and the important
broken S–Zn bond
peaks ofinthe
scatter the S atom
range frommake
−0.25 the
to 1.0SeV.
3pMeanwhile,
orbitals the
noDOSlonger
of 3pbalanced.
y state expandsAsfrom
shown
−5.0 toin Figure 6a,
1.5 eV and its
there are significant split sharp peaks locate in the range from −3.0 to −1.0 eV and from 1.0
of the S 3p states, and the 3py state shows a dramatic difference to 1.5 eV. For the Znwith the 3px
3
center, the sp hybrid orbitals are unbalanced, which will cause a series of changes of the electronic
and 3pz states. For the 3px and 3pz states, their curves cover from −5.5 to 1.0 eV and the important
peaks scatter in the range from −0.25 to 1.0 eV. Meanwhile, the DOS of 3py state expands from −5.0 to
1.5 eV and its sharp peaks locate in the range from −3.0 to −1.0 eV and from 1.0 to 1.5 eV. For the Zn
center, the sp3 hybrid orbitals are unbalanced, which will cause a series of changes of the electronic
 Minerals 2019, 9, 329 9 of 12

cloud distribution. Figure 6b shows obvious divisions of the Zn 3p states. The Zn 3px , 3pz states
present continuous distribution in the range from −2.0 eV to 1.0 eV. The split Zn 3py states seems
apparent difference and its DOS curve continuous from −1.8 eV to 1.5 eV, with a sharp peak next to
Femi2019,
Minerals level.
9, xThe
FORfive
PEERZnREVIEW
3d states exhibit great difference, but have little effect on the S–Zn bonds. 10 of 13

Figure
Figure 6. Projected
6. Projected DOSsof
DOSs ofSS and
and Zn
Znofofsphalerite (110)
sphalerite surface:
(110) (a) S(a)
surface: 3s, S3p3s,
x , 3p
3pyxand
, 3py3pand
z states; (b) Zn (b)
3pz states;
4s, 3p 2 2 2
Zn 4s, 3pxx,, 3p
3pyy and
and3p
3pzzstates;
states;(c)
(c)Zn
Zn3d3d 2–y2and
x x–y and3d
3dz z2states;
states;(d)
(d)ZnZn3d3d
xy ,xy3d and
xz xz
, 3d and3d3d states.
yz yz states.

The bonding and antibonding interactions are distributed in the range from −12.0 to 1.5 eV.
The bonding and antibonding interactions are distributed in the range from −12.0 to 1.5 eV. The
The bonding interactions among S 3s, 3p, and Zn 3p states are provided by S 3s and Zn 3px , 3py , 3pz
bonding interactions among S 3s, 3p, and Zn 3p states are provided by S 3s and Zn 3px, 3py, 3pz states
states in the range from −12.0 eV to −9.7 eV and S 3px , 3py , 3pz and Zn 3px , 3py , 3pz states in the
in the range fromfrom
energy range −12.0 eVeV
−3.0 to to−9.7 eVeV.
1.25 and S 3px, 3py, 3pz and Zn 3px, 3py, 3pz states in the energy range
from −3.0 eVProjected
The to 1.25 eV.
DOSs of O and Zn atoms in the smithsonite (101) surface are shown in Figure 7.
The Projected
Compared DOSs
with the of O and
sphalerite (110)Zn atoms
surface, theinDOSs
the smithsonite
of smithsonite (101)
(101)surface
surface are shown
shows more in Figure 7.
electron
Compared with the sphalerite (110) surface, the DOSs of smithsonite (101) surface
distribution in the lower energy area. The three curves of the O 2p states are quite different, which shows more
electron distribution
indicates in the
that they are splitlower energy
heavily. The 2parea.
x stateThe three curves
expands of the wider,
and becomes O 2p states
while are quite
the 2p y and different,
2pz
seems more localization, the peaks of
which indicates that they are split heavily. Thethe 2p z state in the Femi energy are sharp. The Zn center
2px state expands and becomes wider, while the 2py shows
anda2pspz3seems
hybridmore
orbitals, when the the
localization, O–Zn bondofisthe
peaks broken, the corresponding
2pz state in the Femi energyelectron
arecloud
sharp.interactions
The Zn center
will change. Figure 7b shows
shows a sp hybrid orbitals, when the
3 the 3p x , 3p
O–Zn
y , and 3p
bond states scatter in the range from
z is broken, the corresponding electron -11.5 to 0.5 eV,
cloud
and seldom DOS distributes near Femi level except for the tiny peaks attributing to 3p
interactions will change. Figure 7b shows the 3px, 3py, and 3pz states scatter in the range from -11.5 to x and 3p z states.
Meanwhile, the five 3d states are split significantly, and show complex differentiation in the range
0.5 eV, and seldom DOS distributes near Femi level except for the tiny peaks attributing to 3px and
from −12.5~−10 eV and from −9.5 to −2.5 eV.
3pz states. Meanwhile, the five 3d states are split significantly, and show complex differentiation in
the range from −12.5~−10 eV and from −9.5 to −2.5 eV.
 Minerals 2019, 9, 329 10 of 12
Minerals 2019, 9, x FOR PEER REVIEW 11 of 13

Figure 7. Projected DOS of O and Zn of smithsonite (101) surface: (a) O 2s, 2px , 2py and 2pz states;
Figure 7. Projected DOS of O and Zn of smithsonite (101) surface: (a) O 2s, 2px, 2py and 2pz states; (b)
(b) Zn 4s, 3px , 3py and 3pz states; (c) Zn 3dx 2 –y 2 and 3dz 2 states; (d) Zn 3dxy , 3dxz and 3dyz states.
Zn 4s, 3px, 3py and 3pz states; (c) Zn 3dx –y and 3dz states; (d) Zn 3dxy, 3dxz and 3dyz states.
2 2 2

The complex interactions of O and Zn atoms mainly attribute to O 2p and Zn 3p and 3d states in
The
the complex
range interactions
from −11.5 of O
to −0.5 eV. and
The Zn atoms
bonding statesmainly attribute
locate in the rangetofrom
O 2p−11.5
and to
Zn−10.25
3p and eV,3d states
from
in the range
−9.75 from
to −8.5 eV,−11.5 to −0.5
and −5.5 eV.eV,
to 1.25 The andbonding
contribute states
by Olocate
2s, 2p in
andthe
Znrange
3p, 3d from
states,−11.5 to −10.25
O 2p and Zn 3p,eV,
2 2 and 3d states, and O 2p and Zn 3p , 3p , and 3d states.
from3d−9.75
x -y , to −8.5 xy
eV, and −5.5 to 1.25 eV, andx contribute z by
xy O 2s, 2p and Zn 3p, 3d states, O 2p and
Zn 3p, 3dx2-y2, and 3dxy states, and O 2p and Zn 3px, 3pz, and 3dxy states.
4. Conclusions
4. Conclusion
This study focuses on surface electronic structures of sulfide and oxide minerals. Three pairs of
different minerals are presented and the conclusions can be summarized as follows:
This study focuses on surface electronic structures of sulfide and oxide minerals. Three pairs of
(1) The direction and magnitude of the atomic displacements are affected by the surface broken
different minerals are presented and the conclusions can be summarized as follows:
bonds. Generally speaking, the atomic displacements of the sulfide surfaces is larger than that of the
(1) The
oxide direction
surfaces, and and magnitude
the atoms of the atomic
of the sulfide mineralsdisplacements
surfaces are moreare likely
affected by the surface broken
to reconstruct.
bonds. Generally speaking,
(2) Femi energy theshows
analysis atomic displacements
that the Femi levelof of the sulfide
the oxide surfaces
surfaces is largerless
is generally than that
than of the
zero,
oxide surfaces, and the atoms of the sulfide minerals surfaces are more likely to reconstruct.
while that of the sulfide surfaces are positive numbers, which means that the sulfide surfaces possess
(2) Femi
higher energy
chemical analysis
potential andshows thatlikely
are more the Femi level of donors
to be electron the oxide surfaces is generally less than
in reactions.
zero, while thatprojected
(3) The of the sulfide
DOSs surfaces are positive
investigation shows thatnumbers,
the outerwhich
electronsmeans that the
are easily sulfide
affected, andsurfaces
the
density
possess of states
higher in thepotential
chemical direction and
of broken bonds
are more showtosignificant
likely be electronsplits, especially
donors for their p and d
in reactions.
states.
(3) TheThe S 3p states
projected are the
DOSs mainly contributing
investigation states
shows that theinouter
the sulfide surface,
electrons arewhile
easilythat in the oxide
affected, and the
density of states in the direction of broken bonds show significant splits, especially for their p the
surface are O 2p states. The bonds of the sulfide surface have more covalent features and that of and d
oxide
states. Thesurface are ionic
S 3p states areinteractions.
the mainly The DOSs of the
contributing oxideinsurfaces
states are distributed
the sulfide surface, while in thethat
lower in energy
the oxide
range, which indicates that the bond interactions of oxide surfaces are more stable.
surface are O 2p states. The bonds of the sulfide surface have more covalent features and that of the
oxide surface are ionic interactions. The DOSs of the oxide surfaces are distributed in the lower energy
range, which indicates that the bond interactions of oxide surfaces are more stable.
Author Contributions: Conceptualization and scheme, J.C.; Data curation, Y.Z. and W.C.; Formal analysis, W.C.;
Investigation, W.C., Y.Z., J.C., C.Z., Y.L. and Y.C.; Project administration, J.C.; Software, M.-H.L.; Writing—
original draft, W.C.

Funding: This research is financially supported by the Natural Science Foundation of China (No. 51574092,
Minerals 2019, 9, 329 11 of 12

Author Contributions: Conceptualization and scheme, J.C.; Data curation, Y.Z. and W.C.; Formal analysis, W.C.;
Investigation, W.C., Y.Z., J.C., C.Z., Y.L. and Y.C.; Project administration, J.C.; Software, M.-H.L.; Writing—original
draft, W.C.
Funding: This research is financially supported by the Natural Science Foundation of China (No. 51574092,
51874106) and the Found of State Key Laboratory of Mineral Processing (BGRIMM-KJSKL-2017-03).
Conflicts of Interest: The authors declare no conflict of interest.

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